Acceleration of the speed of seasoning of surface covering compositions



Patented Aug. 11, 1942 ,UNITED ST S v Accsmaarion or '1' :PEEn mistress.

me or SURFACE covsamc- COMPQ1- TIONS Donald G. Patterson, Stamford,-Conn., assignorj to American Cyanamid Company, New York, N. Y., acorporation of Maine No Drawing. Application April 26, 1940, Serial No.331,812

4 Claims. (Cl. 106-264) This invention relates to the acceleration ofthe rate of curing or seasoning" of surface covering compositions suchas floor covering compositions containing siccative binders.

An object of this invention is to provide accelerators for surfacecovering compositions containing siccative binders which will. causesuch compositions to cure more rapidly.

This and other objects are attained by incorporating in a siccativecomposition which is to be used in a floor covering composition or othersurface covering composition a guanamine, i. e., of the probableformula:

Ri\ N/ \N R1 N t J-l .R. R, or the tautomeric forms thereof, wherein R,R1, Ra, Re and R4 may be aliphatic, cycloaliphatic', aralkyl or aryl, orR1, R2, R3 and R4 may be hydrogen, and where at least one of the "R"groups includes at least six aliphatic carbons. Those compounds whereinthe R. containing at least six carbon atoms is a branched chain areespecially useful.

is placed in a stoving oven through which a current of heated air fromabout 70 C. to about 90 C. is circulated until the material iscompletely Thefollowing examples are given by way of il- Thesesubstances. .with or without a small proportion of drier, e. g. 0.1%-cobalt naphthenate, are mixed together, e. g., in an internal mixer.The compacted mass which is delivered from the mixer may bedisintegrated, as by a set of scratch rolls." which comprises aplurality oi'rolls having 'intermeshing teeth projecting from theirsurfaces. The resulting material is sheeted on calender rolls oroptionally it'may be further mixed and disintegrated and thencalendered. The material may be calendered on to burlap or otherseasoned," i. e., until the sheet acquires the necessary degree ofhardness. Higher or lower temperatures may be used if desirable.

The hardness may be measured by any of the methods generally employed inthe manufacture of linoleum. See the Federal Stock Catalogue (U. S.Government Printing Office) section 4, part 5, pages LLL-L-351 et seq.and pages LLL-L-36l et seq., for the method employed herein. The

time required for seasoning"'a 2 mm. sheet of the above composition isabout 5 to 6 days.

The resulting seasoned floor or surface covering has about the samestrength and flexibility as compositions which do not contain the accelerator. Furthermore, surprisingly enough, the

compositions containing the accelerators have slightly lighter colorthan the compositions not containing any accelerator and this is tobe'compared with the darkening effect which is obtained with many otheraccelerators. Not only do many of the other accelerators discolor thesurfacecovering compositions but, in some instances, they also affectthe strengthwand flexibility in such a way as to render the materialscommercially-unsatisfactory. The seasoning speed of a 2 mm. sheet of thesame mixture as employed in this example which does not contain anylauroguanamine is about 18-20 days. I

Example 2 v Parts by weight Binder I 30 Wood flour 30 Whiting 20Lithopone s 20 Lauroguanamine 0.3 This composition may be mixed andsheeted according to the procedure 01' Example 1. The sheetedcomposition seasons in about 4 days and has the same desirableproperties as the compositions produced according to Example 1.

The siccative binder utilized in the above ex- I amples is an alkydresin which has sicca'tive prop- -erties, i. e., a reaction product offumaric acid with a non-coniugatedterpene(alpha pinene) and triethyleneglycol, modified with linseed oil 5 fatty acids. Other similar resinsmay be used which are drying oil-modified reaction products of maleic or'fumaric acids with a terpene and a polyhydric alcohol. Other alkydresins which are modified with drying oils may be used suchas fibrousbacking if desired. The sheeted material the phthalic-glyceride resins,the glycol-maleic resins, and mixed resins such as thephthalicfumaric-glycol-glyceride resins. With other types of binders,the "seasoning temperature may be varied appropriately and, of course,the time required may be different. About the same proportionalaccelerating effect is obtained ,when various siccative binders areemployed.

Other binders which may be used are those which are derived from thedrying oils and may be made in any convenient well-known manner, such asthe method described in British Patent 305,656, or the binders maycomprise any of the various alkyd resins having siccative properties.For drying oil binders, linseed oil is preferable for economic reasonsbut other siccative oils may be used such as, for example, menhaden orfish oil, tung oil, soya-bean oil, perilla oil, oiticica oil, Scheiberoil, sunflower-seed oil, etc. The term siccative oil as used herein isintended to include not only the so-called drying oils but also theso-called semi-drying oils. Furthermore, it is possible to use mixturesof siccative oils with other fatty oils of the non-drying type.

It may be preferable in the manufacture of linoleum to make use ofso-called scrim-oil" or shed oil, either alone or fiuxed with rosin orother gums or resins and/or mixed with a proportion of the so-calledmechanical oil. Either of these types of oils may be used singly if'desired.

In the preparation of the siccative oil binders it is customary to userosin in admixture with the oil although other substances of the sametype may be used, e. g., kauri gum, Congo gum, ester gum, abietic acidand its esters, pimaric acid, etc.

Instead of wood flour and/or the whiting and lithopone used in theexample, other fillers or pigments may be used. Examples of such fillersare: cork, cellulose pulp, asbestos, cottonwood tree pulp, walnut shellmeal, glass fibers, foliated glass, etc. Among the pigments which may beused the following are included: lithopone, barytes, zinc oxide,titanium oxide, chromates, red lead, white lead, malachite green, chromegreen, chrome yellow, Prussian blue, iron oxide, etc. Similarly, dyesand lakes may be used if desirable.

It is generally preferable to use driers in the preparation of thebinders. The drier is usually added to the binder during the oxidationprocess and if desirable, additional drier may be added when the binder,fillers, etc., are mixed together. Suitable driers include theoil-soluble salts such as the naphthenates, resinates and linoleates ofcobalt, lead, manganese, zinc and chromium. Only a small proportion ofthese dries based on the siccative oil content is generally sufficient,e. g., about 0.005 1%, although larger proportions may be used asexpedient. Obviously various mixtures of driers may be used.

The term seasoning" as applied to linoleum compositions indicates theprocess of curing by heating or equivalent treatment to polymerizeand/or oxidize the composition to a stage wherein the floor covering issufliciently hard and resistant to abrasion to be suitable for itsintended purpose and yet is still sufficiently flexible to permit theusual bending and rolling required of linoleum. The term maturing issimilarly used.

Other accelerators which may be used include: ethyl-n-butylacetoguanamine, heptoguanamine (CcHi3C:N3(NH2) 2) 2 (a-ethyl-n-amyl)-4-butylamino-G-amino-1,3,5-triazine, di-n-propyl acetoguanamine, methylisoamyl acetoguanamine, methyl-n-hexyl acetoguanamine, p,p-di-n-propioguanamine, diisobutyl acetoguanamine, namyl-n-heptylacetoguanamine, di-n-heptyl acetoguanamine, di-n-octyl acetoguanamine,etc.

Obviously mixtures of any of these or mixtures containing lauroguanaminemay be utilized in the same way as the single compounds. In someinstances, my accelerators may also improve the alkali resistance.

I have found that only a small proportion of these accelerators isgenerally sufficient, e. g., 0.1- 5% of the siccative composition, butobviously smaller or larger proportions may be used if desirable.

My accelerators are preferably added during the mixing of the binderwith the fillers, etc., although they may be added before or during theoxidation of the binder. If my accelerators are added before or duringthe oxidation they may inhibit somewhat the gelation of the siccativebinder. It is to be noted, however, that after gelation my acceleratorsspeed up the curing of the siccative composition.

Obviously many modifications in the processes and compositions describedabove may be made without departing from the spirit and scope of theinvention as defined in the appended claims.

I claim:

I. In a process of curing a surface covering composition including asiccative material selected from the group consisting of drying oils anddrying oil modified polyhydric alcohol-polybasic acid resins, the stepwhich comprises adding to such a composition a 'guanamine having asubstituent group containing at least six carbon atoms.

2. In a process of curing a surface covering composition including asiccative material selected from the group consisting of drying oils anddrying oil modified polyhydric alcohol-polybasic acid resins, the stepwhich comprises adding to such a composition lauroguanamine.

3. In a process of curing a surface covering composition including asiccative material selected from the group consisting of drying oils anddrying oil modified polyhydric alcohol-polybasic acid resins, the stepwhich comprises adding to such ,a composition ethyl-n-butylacetoguanamine.

4. In a process of curing a surface covering composition including asiccative material selected from the group consisting of drying oils anddrying oil modified polyhydric alcohol-polybasic acid resins, the stepyvhich comprises adding to such a composition 2(-ethyl-n-amyl)-4-butyl-amino-6-amino-1,3,5-triazine.

DONALD G. PATTERSON.

